KR100690099B1 - Flexible fabric from fibrous web and discontinuous domain matrix - Google Patents

Abstract

A composite having a plurality of filaments arranged in a fibrous web that is held together in a unitary structure by a domain matrix. The domain matrix comprises a plurality of matrix islands that individually connect, or bond, at least two filaments, to thereby hold the filaments in a unitary structure. Portions of the filament lengths within the unitary structure are free of matrix islands, causing the domain matrix to be discontinuous. The composite possesses a greater flexibility than coated structures. The composite may be formed into cross-plied structures. A method of making the composite also is disclosed.

Description

FLEXIBLE FABRIC FROM FIBROUS WEB AND DISCONTINUOUS DOMAIN MATRIX}

The present invention relates to a continuous fibrous layer system formed integrally with a material domain forming a matrix island, and more particularly to a continuous fibrous layer system holding together a composition of a matrix island and a matrix island lattice continuous fiber layer system. It relates to a manufacturing method. The fibrous layer system of the present invention provides a high strength composite useful for flexible articles with high axial resistance to warpage and strength properties, especially high impact resistance.

Items designed to be resistant to ballistic impact are known, such as bulletproof vests, helmets, body armor, armor plates and other police and military devices, helicopters, aircraft, ship and vehicle panels, and briefcases containing high strength fibers. Known high strength fibers include fibers such as aramid fibers, poly (phenylenediamine terephthalamide), ultra-high molecular weight polyethylene, carbon fibers, ceramic fibers, nylon fibers, glass fibers and the like. The fibers are generally encapsulated or embedded in a continuous matrix material structure, and in some cases form a complex composite structure with hard facing. Body armor should provide protection against ballistic projectiles such as bullets and similar pierced or projectile states. However, body armor, bulletproof vests and the like may be strict and limit the wearer's movement.

Ballistic-resistant composites are described in US Pat. No. 4,403,012; 4,501,856 and 4,563,392 to Harpell et al. This patent discloses a high strength fiber mesh in a matrix composed of olefin polymers and copolymers, unsaturated polyester resins, epoxy resins and other resins curable under the melting point of the fibers thereof. Such composites provide effective ballistic resistance, while "The Effect of Resin Concentration and Laminating Pressures on Kevlar Fabric Bonded with Modified Phenolic Resin" (ALLastnik et al., 1984, 6, 8), Technical Roport NATICK / TR-84 / 030 discloses that interstitial resins, which encapsulate and bind fibers in the fabric, reduce the ballistic-resistance of the resulting composite. Therefore, it is necessary to improve the structure of the composite in order to effectively use the properties of high strength fibers.

U. S. Patent No. 4,623, 574 to Harpell et al., Filed 1985,1, 14, discloses a simple composite comprising high strength fibers embedded in an elastomeric matrix. Surprisingly, the simple composite structure exhibits very good ballistic protection compared to the simple composite using the resulting rigid matrix disclosed in the patent. In particular, simple composites using ultra-high molecular weight polyethylene and polypropylene as disclosed in US Pat. No. 4,413,110 are effective.

In general, composites having continuous domains in which the percentage of resin is limited to at least 10% by volume of the fiber content are disclosed in the art. U. S. Patent No. 4,403, 012 discloses a matrix which is preferably present in the range of 10-50% by weight of the fibers. U.S. Patent 4,501,856 discloses a preferred fiber network content of 40-85% by volume of the composite. No. 4,563,392 does not disclose any range of amounts of matrix components. It is desirable to keep the volume and / or weight percent of the fibers in the resulting composite as high as possible to increase ballistic resistance.

U.S. Patents 5,061,545 and 5,093,158 disclose fiber / polymer composites having non-uniformly distributed polymer matrices and methods of making the composites. This patent refers to a fibrous network having a mesh of unidirectional fibers and a non-uniform but continuous matrix composition distributed over the main face of the fibrous network. Although the fibrous web is enclosed in a matrix composition and distributed non-uniformly, the matrix composition remains in engagement with all the fiber members of the fibrous network. The patent discloses a polymeric composition which is non-uniformly distributed with the fibrous mesh such that there is a patterned surface such that some of the resulting bonded nets have a greater amount of polymer than others. Thus, the total amount of polymer required to maintain the integrity of the mesh into which the polymer is incorporated has been reduced. The patent further discloses that thick areas providing the integrity of the polymer layer preferably provide a continuous area along the surface of the fiber / polymer composite.

Other patents, such as US Pat. No. 4,623,574, present difficulties in producing composites of fibrous mesh in a polymer matrix. In Table 6, Sample 12 cannot be tested due to lack of consolidation of the sample in which a large amount of fiber is used.
U. S. Patent No. 3,686, 048 discloses a composite comprising a plurality of parallel fibers in which two or more adjacent filaments are held together by a resin filament.

Cost and quality of fabric also affect the usefulness of body armor. Typical fabric costs rise dramatically as the yarn denier is reduced. Ballistics performance and flexibility are also improved as the area density of each layer decreases.

The present invention is a composite comprising a fibrous network and a discrete domain matrix, preferably a polymeric composition. The domain matrix provides matrix islands or anchor points anchored in the fiber network to allow portions of the fiber network to be joined in a uniform structure. The matrix islands may be attached as much as possible, such as all the filaments of the filament, including as few as possible, such as two filaments in the fiber, or in the form of a continuous string (high stretching domain). By sufficient number, size, shape and distribution of matrix islands each filament in the fiber network forms a uniform structure.

A fibrous web is a layer defined by a number of fibers. Typically, the layer is defined as a surface that is thin and has a depth of at least one filament. Preferably, the fibrous network is a tape or layer in which the fibers are mono-oriented. Uni-directional means that the fibers are parallel to each other in the network or the fibers extend along a given direction axis without overlapping. A matrix island is defined as a fixation point that fixes, preferably joins, each matrix island that is separate or discontinuous from other matrix islands that form a spatial distribution with two or more filaments. Collectively, the matrix islands constitute a domain matrix into which the fiber network binds as a uniform flexible structure. The matrix islands may be distributed in the domain matrix in a regular and / or irregular pattern. The amount of polymeric material of the domain matrix is small so that there can be a fiber zone without matrix (hereinafter referred to as "uncoated fiber" or "uncoated filament"). The fiber network can be cross-plied to form a flexible panel.

The present invention is essentially parallel to each other, preferably a plurality of fibers arranged along a single direction axis and a minimum of the plurality of fibers to fix, preferably join, the plurality of fibers such that the plurality of fibers is of a single structure. Composites comprising matrix islands intersecting some, wherein a number of fibers have out-of-plane flexibility.

In addition, the present invention provides a method of arranging a plurality of fibers in a layer and a plurality of fibers such that each matrix island intersects with a plurality of fibers in sufficient portions such that each matrix island is fixed, preferably joined in a single structure. A method of making a fiberglass composite bridged with a matrix island, comprising disposing a plurality of matrix islands within.

The composites of the present invention can form flexible tapes, preferably unidirectional tapes (also referred to as uni-tapes), which can be used as precursors in conventional textile processes of tape laying or filament winding. have. The cross-sectional shape of the composite can vary depending on the application, such as flat ribbon form, oval, round and specific forms desired for a given fabric process, such as braiding and knitting. The layers of flexible prepreg can be combined to form a cross-ply product.

The composites and methods of the fibrous mesh and matrix domains of the present invention significantly improve the volume ratio of fiber to polymer than is already known in the art while maintaining network integrity. This structure has the ability to deliver water vapor and has ballistic efficiency and high flexibility.

1 is a plan view of a preferred fibrous network having random matrix islands forming a mono-directional structure;

1A shows the domain matrix of FIG. 1;

2 is a plan view showing a domain matrix of uniform matrix islands that engage filaments in a uni-directional structure;

3 is a plan view showing the shape of a matrix island along the length of two unidirectional tapes of FIG. 1 that are 90-degree cross-ply;

3A is a diagram illustrating the form of a single matrix island;

FIG. 4A is an exploded perspective view showing a 0/90 composite structure cross-flyed from two layers of the structure of FIG. 1; FIG.

4B is a top view of FIG. 4A;

4C is a side view of FIG. 4A;

5A is a side view of FIGS. 4A-4C with an outer membrane layer;

5B is an exploded perspective view of FIG. 5A;

6 is a plan view showing a cross-ply structure of a uni-directional tape;

7 shows a preferred method of making a composite of the present invention;

8 is a view showing another preferred method for producing a composite of the present invention.

The present invention relates to a composite having a filament defined by a fibrous web fixed by a domain matrix. The composite preferably comprises a plurality of filaments in the form of parallel fibers, which are regarded as parallel filament arrays fixed to the domain matrix. The domain matrix preferably consists of a polymeric material and consists of a plurality of matrix islands spatially distributed within the domain matrix. The matrix islands are fixed to each other to maintain the filaments of the fiber network in a single structure. Such anchors anchor the filaments of each of the fibrous meshes locally, but the bonds can be bent. The total volume of the matrix islands for a given area of the fiber network, taken as the fiber volume fraction, is defined as the volume ratio density (V _m / V _f ) of the domain matrix.

The matrix islands of the domain matrix are not physically connected to anything other than the filament material. As such, the domain matrix comprises a discontinuous polymeric material or “island”. However, as the matrix islands permanently fix specific fiber locations, the domain matrix is a fixed structure. The discontinuous structure of the domain matrix results in a larger volume percentage of fibers in the composite than the continuous matrix composition. In addition, a robust structure is produced. That is, the domain matrix combines with the fibers in a single structure that is easily manipulated without the tendency to separate or disperse.

The discrete structure of the domain matrix creates an isolated domain in the prepreg and the product made therefrom. The isolated domain, leaving a major portion of the fiber uncoated or matrix free, is necessary to increase the bending of the composite. The amount of domain matrix used should be small enough to provide uncoated filament segments in the prepreg and the resulting product, and may include amounts that increase the area where the matrix is absent. The volume ratio (V _m / V _f ) may be as high as 0.5, long enough to adequately produce the uncoated filament portion of the fiber and polymeric material. However, the domain matrix may preferably be present in a volume ratio of about 0.4 or less, more preferably about 0.25-0.02, and most preferably about 0.2-0.05. The spatial distribution of the matrix islands incorporates very high fiber volumes to form structures with improved physical integrity during processing and use, such as manipulation and cutting of the composite and stacking of unidirectional prepreg tapes. Can be. The resulting fibrous network structure maintains the flexibility of the uncoated fibers bonded within the fibrous network. Maintaining its integrity and operability means that the fiber polymer composite maintains its structure without yarn separation during processing and use. One or more layers of fiber mesh combined with resin can be formed to form various multilayer laminates such as 0/90, + 45 / -45, + 30 / -30, 0/60/120, 0/45/90/135, etc. have. It has been found that such multilayer composite laminates are resistant to impacts, more specifically ballistic impacts.

Each fibrous section of the composite according to the present invention provides a region with and without a polymeric material and polymers or matrices that secure (preferably bond) two or more filaments from each other from the fibrous network. It has a spatial distribution of Ireland.

1 shows a composite 10 comprising a fibrous network 12 and a domain matrix 14. The fiber network 12 consists of filaments 16 arranged in a single-direction. Compared to each matrix island 18, the domain matrix 14 shown separately in FIG. 1A is structured within and defined by the fiber network 12. As shown in Figures 1 and 1A, it is the location of filament 16 that defines the location of matrix island 18 even though the domain matrix 14 binds each filament 16.

As noted above, domain matrix 14 is formed by the bonding of matrix islands 18 and exists as a discontinuous matrix of polymeric material. Uncoated filament 16 secured by matrix island 18 allows the prepreg to achieve dimensional flexibility that is not known in the art. The structure of the present invention can deliver gases and liquids. Further, the matrix-free portion may be filled with other resins to achieve the desired physical properties or properties of the composite.

In one embodiment, matrix island 18 is irregularly and / or non-uniformly arranged in fiber 12 over the length of the fiber 12. Each matrix island 18 has a mutual position of at least two filaments 16 and may have a mutual position of both filaments 16 in a single-directional tape. The excess polymeric material tends to fill the void portions of the fiber 12 so that the matrix island 18 is no thicker than the bundle of filaments 16 in the net 12. Collectively, the irregular matrix island 18 provides a support domain matrix 14 that maintains the fiber network 12 in a single structural form. Other sections of the fibrous network 12 may have different amounts of polymeric material depending on the size and / or spatial density of the matrix 18. However, a given fiber network 12 generally has an average size, size distribution, average distance between matrix islands 18 and other statistical properties of matrix islands 18 over the entire length of the composite providing particular properties. The size of the matrix island 18 also depends on the size of the impact projectile, such that the smaller matrix island 18 better controls the designed parallel spatial position of the filaments positioned in close proximity to the scale of the impact projectiles. In relation to it should be relatively small.

Matrix island 18 should be small compared to the radius of curvature desired from the particular fabric. The uncoated filaments 16 between the matrix islands 18 give the flexibility of the fibrous network 12, while the parts constituting the matrix 18 are fixed to each other to become anchor points for maintaining a plurality of filaments within the fibrous network 12. Preferably, the average size of the matrix islands is less than about 5 mm, more preferably less than about 3 mm, even more preferably less than about 2 mm and most preferably less than 1 mm in at least one direction. Although the portion with the polymer composition is not as flexible as the matrix-free portion, the region with the polymer composition preferably gives flexibility to the fiber 12. Most of the filament 16 lengths are preferably matrix-free (matrix-free) and consequently the fiber network 12 of the present invention can move more easily than the network when the fiber is completely wrapped in the matrix.

In another embodiment, shown in FIG. 2, matrix island 18 is evenly disposed within fiber 12 in a portion of the discrete (discriminated) domain matrix 14 over the length of fiber 12. The spatial density of the matrix islands 18 is generally kept constant over the elongated equivalent length, represented by the length A of the fiber network 12. However, the spatial density of the matrix island 18 can vary greatly over the shorter length of the fiber 12, represented by the length B. Domain matrix 14 may be continuous from one side to the other side of the uni-directional tape as shown in FIG. 2.

The shape of the matrix islands 18 generally follows the surface line of the fiber, as in FIG. 3 where matrix islands 18 on the upper filament 16 are solid and matrix islands 18 on the bottom filament 20 are broken. The size of matrix islands 18 between filaments 16 is on average sufficient to bond adjacent layers and maintain structural integrity in use. The uncoated filaments in the final product are formed depending on the size, shape and spatial density of matrix island 18 in the fibrous net or prepreg. The form of matrix island 18 provides a degree of bending that can be tolerated for a given section of fibrous network 12 while retaining the functional properties as a fixation point for each filament 16. The size of the individual matrix islands 18 is not generally important, but on average the amount of matrix composition should be sufficient over the fixation point to provide structural integrity and strength for a given application. The spatial distribution of the matrix island 18 provides structural integrity at a particular angle perpendicular to the direction of the filament 16 or at other angles, while the spatial density provides the unique properties of a single fiber network 12.

As shown in FIG. 3, the shape of each matrix island 18 extends in length along or parallel to the length of the filament 16. The extended form of the matrix island 18 is due to the phenomenon of wetting upon contact of the filament with a matrix droplet (latex suspension in water or matrix solution). The droplets then spread in the spaces between the filaments to reduce surface energy. As shown in FIG. 3A, the aspect ratio, or length and width ratio (d / w), of the matrix island 18 may be useful over a wide range of amounts, depending on the particular application, but is not limited thereto. 35: 1-1: 1, about 20: 1-1: 1, about 10: 1-1: 1 and about 3: 1-1: 1.

The elongated form is the most common but not limited to regular and irregular forms, including regular forms such as donuts or atolls, rectangles, squares, circles, ellipses, and irregular forms such as asymmetric islands. Can be. The matrix islands, along with the cross filaments 20 used as cross-ply composite structures 30, extend along the length of both filaments 16 and 20 and are both attached thereto. The diameter of the matrix island 18 at the intersection 22 between the filament 16 and the intersecting filament 20 determines the sticking of the single-directional panel (or fibrous network) when formed in the cross-ply configuration. Uni-tape and cross-ply forms of the present invention provide a highly flexible, porous structure. When a single-directional tape having a polymeric material protruding on one side cross-plies with a second single-directional tape, each particle of the polymeric material is pressed into both single-directional tapes. The resin, preferably the resin flowing along the fiber direction of each single-directional tape, forms a cross shape. At each surface of the extended domain, the extended domain is formed with long axes parallel to the fiber direction. Domains extending to 0/90 or + 45 / -45 panels are superimposed and arranged at right angles to each other.

4A-4C show a preferred embodiment of the single-directional tape of FIG. 1 formed in cross-ply form. As shown in FIG. 4A, the tapes 32 and 34 are layered perpendicular to each other for each filament, for example in an 0/90, + 30 / -60 or + 45 / -45 arrangement. Matrix islands 18 forming domain matrix 14 not only bind filament 16 to unidirectional tapes 32 and 34, but also to the tapes 32 and 34. Additional tapes may be placed on one or both sides of the tapes 32 and 34 in the same or different directions, such as in the form -45 / + 45. 4B is a plan view of FIG. 4A showing an upper tape 32 having a matrix island 18 in a discontinuous pattern. 4C is a side view of FIG. 4A showing filament 16 of top tape 32 and bottom tape 34 bonded to matrix island 18.

As shown in Figures 5A and 5B, in some cases it is desirable to have a surface film on the panel to reduce the possibility of catching single fibers and filaments or damaging the panel. 5A shows a side view of an upper tape 32 and a bottom tape 34 made of filament 16 positioned between two films 100 and 102. Tapes 32 and 34 and films 100 and 102 are joined together by matrix islands 18 and collectively form the domain matrix of the composite. FIG. 5B is an exploded perspective view of FIG. 5A, showing tapes 32 and 34 fixed to matrix island 18 with top layer 100 and bottom 102 films fixed to matrix island 18. For maximum flexibility, the film is preferably thin and spot bonded to the tape.

), 바람직하 게 약 10-170도, 보다 바람직하게 약 30-150도의 각을 이루거나 다원(multiple circles), 타원, 난형 및 기하학적 형태로 형성된 패턴을 포함하는 곡선을 이룬다. 6 shows a cross-plied structure with matrix islands 18 extending across the width of tape 34. Extended matrix islands 18 remain discontinuous with each other even when the second tape is applied. The highly elongated narrow matrix domains 14 that traverse linearly across multiple parallel fibers to all parallel multiple fibers in a uni-directional tape are perpendicular to the fiber set or angle (

), Preferably about 10-170 degrees, more preferably about 30-150 degrees, or a curve comprising patterns formed in multiple circles, ellipses, ovals and geometric shapes.

The high strength fibers of the present invention preferably have a stretch modulus of at least about 160 g / denier and a toughness of at least about 7 g / denier in a suitable polymeric matrix or domain matrix 14. The polymer composition of domain matrix 14 may comprise an elastomer, a thermoplastic elastomer, a thermoplastic resin, a thermoset resin and / or a combination or mixture thereof. Preferably the polymer composition comprises an elastomeric matrix material. The fibers are tested according to ASTMD 2256 using 4D tires and cord clamps at 100% / minute stretching in an Instron RTM test machine. It is preferred to have an elastomeric composition having an elongation modulus of less than 20,000 psi, preferably less than 6000 psi, as measured according to ASTM D638-84 at 25 ° C.

The filaments 16 of the present invention are elongated sieves with significant length dimensions relative to their width and thickness transverse dimensions. The term fiber includes, but is not limited to, monofilaments, multifilaments, yarns, ribbons, strips, and structures with regular or irregular cross-sectional areas. For the purposes of the present invention the fiber network 12 comprises any group of fibers useful for forming uni-directional tapes and / or cross-ply structures. Preferred fibrous network 12 includes highly oriented ultra high molecular weight polyethylene fibers, high oriented ultra high molecular weight polypropylene fibers, aramid fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polybenzoxazole (PBZO) fibers, Polybenzothiazole (PBZT) fibers, glass fibers, ceramic fibers or combinations thereof. Ultra-high molecular weight polyethylene is generally understood to include molecular weights in amounts of about 500,000 or more, more preferably about 1 million or more and most preferably from about 2 million up to about 5 million. The elongation modulus of the fibers measured by an Instron elongation test machine is generally at least about 300 g / denier, preferably at least about 1,000 g / denier and most preferably at least about 1500 g / denier. The toughness of the fibers is generally at least 15 g / denier, more preferably at least about 25 g / denier, even more preferably 30 g / denier and most preferably at least about 35 g / denier. The average molecular weight of the ultra-high molecular weight polypropylene is about 750,000 or more, more preferably about 1 million or more and most preferably about 2 million or more. Because polypropylene is significantly less crystalline than polyethylene and contains pendant methyl groups, the tenacity value that can be achieved with polypropylene is generally substantially lower than that corresponding to polyethylene. Suitable toughness for the polypropylene may range from at least about 8 g / denier, preferably at least 11 g / denier. The elongation modulus for polypropylene is at least about 160 g / denier, preferably at least about 200 g / denier. The melting point for polypropylene is generally raised by the orientation process such that the polypropylene fibers preferably have a main melting point of at least about 168 ° C, more preferably at least about 170 ° C.

29, Kevlar

49 및 Kevlar

129로 제조되는, 폴리(-페닐렌디아민 테레프탈아미드) 섬유를 포함한다.Aramid fibers are basically formed from aromatic polyamides. Aromatic polyamide fibers having at least about 400 g / denier elongation modulus and at least about 18 g / denier toughness are useful for incorporation into the composites of the present invention. For example, aramid fibers are sold under the trade name Kevlar from DuPont Corporatio (Wilmington, Delaweare).

29, Kevlar

49 and Kevlar

Poly (-phenylenediamine terephthalamide) fibers, made from 129.

It is useful that the polyvinyl alcohol (PV-OH) fibers have a weight average molecular weight of at least about 100,000, preferably at least 200,000, more preferably about 5,000,000-4,000,000 and most preferably about 1,500,000-2,500,000. The PV-OH fibers available are at least about 60 g / denier, preferably at least about 200 g / denier, more preferably at least about 300 g / denier elongation modulus and at least about 7 g / denier, more preferably at least about 10 g / dinier, more It should preferably have a toughness of at least about 14 g / denier and most preferably at least about 17 g / denier. PV-OH fibers having a weight average molecular weight of at least about 500,000, toughness of at least about 200 g / denier and modulus of at least about 10 g / denier are particularly useful for the production of ballistic resistant composites. PV-OH fibers having such properties can be produced, for example, by the process disclosed in US Pat. No. 4,559,267 to Kwon et al.

Details of the filaments of polybenzoxazole (PBZO) and polybenzothiazole (PBZT) are described in Part D of "The Handbook of Fiber Science and Technology: Volume II, High Techonology Fibers." (Menachem Lewin). .

Polyacrylonitrile (PAN) fibers having a molecular weight of at least about 400,000 and preferably at least 1,000,000 may also be used. Particularly useful are PAN fibers having a stiffness of at least about 10 g / denier and a breakdown energy of at least about 22 joule / g. PAN fibers having a molecular weight of at least about 400,000, a stiffness of at least about 15-20 g / denier and a breakdown energy of at least about 22 joule / g are most useful for producing ballistic resistant articles, such fibers are disclosed, for example, in US Pat. No. 4,535,027. It is.

For the purposes of the present invention, the fibrous layer comprises at least one fibrous network of fibers alone or of fibers having a matrix. The fiber comprises one or more filaments 16. Fiber refers to an elongate body having a length dimension that is significantly greater than the transverse dimension of the width and thickness. Thus, the term fiber includes monofilaments, multifilaments, ribbons, strips, staples and other forms of chopped, cut or discontinuous fibers and those having regular or irregular regular cross sections, and the like. The term fiber includes a plurality of any one or a combination thereof.

The cross section of the filament used in the present invention can vary widely. They may be circular, flat or oblong in cross section. They may also be irregular or regular multi-lobe cross sections with one or more regular or irregular lobes projecting from the linear or longitudinal axis of the fiber. The filament is particularly preferably substantially circular, planar or rectangular in cross section and most preferably in circular cross section.

The fibers may be arranged in a fiber network having various shapes. A fibrous network means a network of fibers arranged in a predetermined form or a plurality of fibers or a plurality of fibers grouped together to form twisted or untwisted yarns arranged in a predetermined form. do. For example, the fibers or yarns may be arranged in parallel, layered, or felt formed of a fabric by any of a variety of conventional techniques, or other nonwovens, knits, or fabrics (planes, baskets, satin and crow pits). Etc.). Among these techniques, due to ballistic resistant applications, we prefer to use an arrangement in which the fibers are flattened so that essentially each filament forms a single layer. Other fiber arrangements can be used for cut or slash resistant applications. According to a particularly preferred network configuration, the fibers are arranged in a single direction such that they are substantially parallel to each other along the usual fiber direction. Fibers of continuous length are most preferred, but fibers oriented and having a length of about 3-12 inches (about 7.6-30.4 cm) are also acceptable and are considered "substantially continuous" for the purposes of the present invention.

Both thermosetting resin and thermoplastic resin particles can be used in the present invention, alone or in combination. Preferred thermosetting resins include epoxies, polyesters, acrylics, polyimides, phenols and polyurethanes. Preferred thermoplastics include nylon, polypropylene, polyesters, polycarbonates, acrylics, polyimides, polyetherimides, polyaryl ethers and polyethylene and ethylene copolymers. Thermoplastic polymers have improved environmental resistance, burst strength and impact strength compared to thermoset materials. Prepregs with thermoplastic domain matrices have a long shelf life and are resistant to environmental concerns with regard to storage. The high viscosity of the thermoplastic polymer does not affect the discontinuous application of the polymeric material into the fiber network 12. Even at significantly increased amounts, the thermoplastic prepregs of the present invention are flexible structures. Prepregs containing thermosetting domain matrix 14 are relatively flexible and viscous prior to reaction.

D1650 분말, 또는 LDPE(저 밀도 폴리에틸렌) 또는 LLDPE(선형 저 밀도 폴리에틸렌)의 분말을 갖는 Kraton

D1650 분말과 215 denier Spectra

1000 섬유로된 섬유망 12을 함께 사용하여 120℃에서 성형하여 제조될 수 있다. 이러한 이유로, 통상적으로 상업용 단일 성분으로 사용되는 폴리에틸렌 필름에 대한 필요성이 제거될 수 있다.The domain matrix may comprise a polymeric material selected from polymeric powders, polymeric solutions, polymeric emulsions, chopped filaments, thermosetting resin systems, and combinations thereof. Application of such polymeric materials can be by spraying, droplets, emulsions and the like. If chopped filaments are used, heat and / or pressure may be used to coalesce the uni-tape and / or multilayer panel and the chopped filaments should be melted at a temperature lower than the melting point of filament 16 of the uni-tape. The flexible structure is for example Kraton

Kraton with D1650 powder, or powder of LDPE (low density polyethylene) or LLDPE (linear low density polyethylene)

D1650 powder and 215 denier Spectra

It can be produced by molding at 120 ° C using a fiber net 12 of 1000 fibers together. For this reason, the need for polyethylene films that are typically used as commercial single components can be eliminated.

If desired, the preformed fibers may be precoated with a polymeric material (preferably elastomer) before being arranged in a network as described above. The elastomeric material, which can also be used as a matrix, has a tensile modulus of less than about 20,000 psi, preferably less than 6,000 psi (41,400 kPa) as measured at about 23 ° C. Preferably, the more desirable improved performance is that the tensile modulus of the elastomeric material is less than about 5,000 psi (34,500 kPa), most preferably less than about 2,500 psi (17,250 kPa). The glass transition temperature (Tg) of the elastomer, which is the elastomeric material (as evidenced by the sudden dropwise addition to the flexible and elastic material), maintains flexibility under field or working conditions including less than about 25 ° C or less than about 0 ° C. . Tg of the elastomer may be in a range of less than about −40 ° C. or less than about −50 ° C. as necessary. The elastomer has a fracture elongation of at least about 50%. Preferably, the fracture extensibility is at least about 100% and more preferably about 150%.

Any elastomeric material suitable for forming the domain matrix can be used in the present invention. Representative examples of suitable elastomers which are such elastomeric materials are formulations by structures, properties, and cross-linking processes summarized in Encyclopedia of Polymer Science, Volume 5, "Elastomers-Synthetic" (John Wiley and Sons Inc., 1964). Has For example, any of the following materials may be used: polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylenepropylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, chlorosulfonated Polyvinylchloride, butadiene acrylonitrile elastomer, poly (isobutylene-co-isoprene), polyacrylate, polyester, plasticized using polyethylene, polychloroprene, dioctyl phthalate or other plasticizers well known in the art , Polyethers, fluoroelastomers, silicone elastomers, thermoplastic elastomers, copolymers of ethylene. Particularly useful elastomers are block copolymers of conjugated dienes and vinyl aromatic monomers. Butadiene and isoproprene are preferred conjugated diene elastomers. Styrene, vinyl toluene and t-butyl styrene are preferred conjugated aromatic monomers. Block copolymers incorporating polyisoprene can be hydrated to produce thermoplastic elastomers having saturated hydrocarbon elastomer fragments. The polymers are simple tri-block copolymers of type ABA, multi-block copolymers of type (AB) n (n = 2-10) or radial forms of type R- (BA) x (x = 3-150). May be a copolymer of wherein A is a block of polyvinyl aromatic monomer and B is a block of conjugated diene elastomer. Many such polymers are commercially produced by Shell Chemical Co and described in "Kraton Thermoplastic Rubber", SC-68-81.

Most preferably, the elastomeric material comprises one or more of the elastomers. Low modulus elastomeric materials may also include fillers such as carbon black, silica, glass micro-balloons, etc. in an amount of no greater than about 300 weight percent of the elastomer, preferably in an amount of no greater than about 100 weight percent. And can be stretched using a radiation curing system using methods well known to those skilled in the art of sulfur, peroxides, metal oxides or rubber. Mixtures of different elastomeric materials may be used together or one or more elastomeric materials may be mixed with one or more thermoplastics. High density, low density and linear low density polyethylene can be used to crosslink to obtain materials of suitable properties alone or in combination.

The proportion (vol%) of polymeric material to the fiber or fabric depends on the strength, shape, heat resistance, wear resistance, flame retardancy and other desired properties. Other factors affecting these properties include the spatial density of the domain matrix, the percent voids in the fiber network, the uniformity of the matrix islands and other variables related to the placement, size, shape, location and composition of the polymeric material and fibers. Include them.

A particular preferred method of making the composite of the present invention is shown in FIG. This is a method of making a composite comprising a fiber network in which the fibers are unidirectionally oriented. Filament 16 is rolled onto polyethylene film 102 to form fibrous network 12. Elastomers, thermoplastic elastomers or thermoplastic precursors forming domain matrix 14 are sprayed onto the fibrous network 12. After being sprayed, fiber 12 with domain matrix 14 precursor is fed to oven 50 to provide a bond between fiber 12 and domain matrix 14 precursor. After cooling, a single-directional tape 52 is formed. Polymerization solutions can be used in a similar manner. Thermosetting resins and monomers can be sprayed onto the fiber 12 and subsequently reacted. The pattern of the domain matrix 14 can be adjusted using a mask or mold, such as using a series of parallel wires to screen a continuous length with a narrow width of less than 200 microns.

In addition, geometry can be used to form a flexible structure using three sets of parallel seams, as disclosed in US Pat. Nos. 5,316,820 and 5,362,527. However, any method can be used with any fibrous network.

On the other hand, polymeric latex can be applied onto the fiber network 12 and subsequently bonded to the fiber network 12 with heat and / or pressure. As shown in FIG. 8, the fiber network 12 may be in contact with the pressure roll 200 supplied from the container 202 of the latex 208. Fiber 12 passes through the nip between 200 pressure rolls. The pressure roll 200 is immersed in the container 202 and the latex 208 adheres to the same pattern as the continuous line 204 or spot 206 in the pressure roll 200. As the uni-directional tape is in contact with the latex 208 coated pattern of the pressure roll 200, the polymer is transported onto the fiber network 12 to form matrix island 18. Fiber net 12 with attached matrix island 18 can then be heated if desired.

A finite amount of polymer is collected in fiber 12. The amount allows the regions free of polymer to form in the prepregs or tapes formed therefrom and their final products. Generally the amount of the polymer is about 50% or less, preferably about 20% or less, more preferably about 20-2%, even more preferably about 15-5% and most preferred of the filament 16 surface area of the fiber 12 About 10-5%.

The discontinuous distribution of the matrix composition can be made by other means. For example, the present invention includes spot laminating a fibrous network with a polymer of at least one non-continuous layer of polymer. This may be applied by feeding the polymer on the first layer in a discontinuous form or by precoating or by using a region without polymer and the region with the polymer, i. The discontinuous polymer layer can be laminated using the fiber network under heat and pressure, resulting in a discrete domain matrix in the fiber network. This allows the fiber mesh to be held in position by the domain matrix such that discrete matrix islands are formed with voids therebetween. The composite may contain as little as 2% by volume of resin (matrix), which is sufficiently distributed so as to maintain the integrity of the fiber network despite solid percent fibers, or to form voids between the filaments of the fiber network. A sufficiently distributed resin may contain as much as about 50% by volume.

The matrix may be applied to the fibrous network in various ways, such as particles in a liquid, viscous solid or suspension or fluid bed. The matrix can also be applied as a solution or emulsion in a suitable solvent that does not adversely affect the properties of the fiber network. Appropriate application of the matrix includes printing, spraying, slurry, and / or electrostatic printing, and / or other suitable matrix application using a type of application in a particular situation that can be determined by one skilled in the art. do. While any liquid capable of dissolving or dispersing the matrix polymer may be used, preferred solvent groups include hydrocarbon solvents including water, paraffin oil, ketones, alcohols, aromatic solvents or paraffin oils, xylenes, toluene and octane. do. Techniques used to dissolve or disperse the matrix polymer in the solvent are those commonly used to coat similar elastomeric materials on various substrates.

Another technique for applying the polymer (matrix) to the fiber may include coating a high modulus precursor (gel fiber) in a hot stretching operation, either before or after removing the solvent from the fiber. The fibers are then stretched at elevated temperatures to form coated fibers. The gel fibers can be passed through an appropriate coating polymer solution (solvent can be paraffin oil, aromatic or aliphatic solvent) under conditions to obtain the desired coating. The polymer polyethylene may or may not crystallize in the gel fibers before the fibrous network passes through the cooling solution.

The fibers and meshes produced therefrom may be formed from composite materials used as precursors or prepregs in the manufacture of composite articles. The low surface density prepreg of the present invention can be used to produce coalesced panels that provide good ballistic protection. The term composite refers to the combination of fibers or fabrics with polymeric materials in the form of matrix islands, which may include fillers, lubricants or other materials such as those mentioned above.

Other methods of fixing domain matrix 14 include, but are not limited to, hot melt, solution, emulsion, slurry, surface polymerization, fiber commingling, film insertion, electroplating and / or dry powder techniques.

Composite materials can be constructed and arranged in various forms. It is convenient to characterize the geometry of such composites according to the geometry of the fibers and then indicate that the matrix material can occupy some or all of the void space left behind by the mesh of fibers. One such suitable arrangement is a plurality of laminate layers in which the coated fibers are arranged in a sheet-like arrangement and arranged parallel to one another along the same fiber direction. The continuous layer of such coated unidirectional fibers can be rotated relative to the previous layer. Examples of such laminate structures are composites having a second layer, a third layer, a fourth layer, and a fifth layer rotated + 45 °, -45 °, 90 °, and 0 ° relative to the first layer, arranged in order It doesn't have to be. Other examples include composites with other layers rotated 90 ° with respect to each other, for example 0/90, + 45 / -45, + 30 / -60 and the like. The present invention includes a composite having a plurality of layers. These may be 1-500, preferably 2-100 and more preferably 2-75 layers.

A common technique for forming laminates includes arranging the coated fibers into a desired mesh structure and then coalescing and heating the entire structure to allow the coating material to flow and occupy a fraction between the pores to form a continuous matrix. Another technique is to coalesce and thermoset the entire structure after the coated or uncoated fibers are arranged adjacent to the matrix material or in layers or other structures between various forms such as, for example, films. In such a case, the matrix may be viscous or flowable without completely melting. In general, if the matrix material is only heated to a sticking point, higher pressures are generally required. In addition, the pressure and time to fix the composite and to have optimal properties generally depends on the nature (chemical composition and molecular weight) and process temperature of the matrix material. For the purposes of the present invention, substantial void (matrix-free) volume should be maintained.

Multiple tapes containing the composite 10 of the present invention may be bonded to each other. US Pat. Nos. 5,061,545 and 5,093,158 disclose various combinations of two layer composites in which the fibers in each layer are unidirectional fibers. The fibers in adjacent layers are disclosed to be angled at 45-90 ° to each other, preferably at about 90 ° to each other. These are disclosed in US Pat. Nos. 5,061,545 and 5,093,158, which are incorporated herein by reference.

The fiber content of the composite of the present invention is very high, 90-98% by volume, and has an improved ballistic effect compared to composites having a continuous polymerization matrix. Not only is it useful for commonly known articles designed to prevent ballistic impacts, such as bulletproof vests, helmets and body armor, the present invention is particularly effective against micro meteorites and explosions and / or very fast impacts as large as about 7 km / s. It is useful in space environments where ballistic impacts can occur.

Experiment method

Step A. Preparation of the Dry Fiber Network

필름(AlliedSignal Specialty Flm 제품, of Pottsville, Pennsylvania)으로 쌌다. 폭 2인치(5.08cm) 더블 스틱 테이프 스트립이 상기 드럼의 축에 평행하게 중심대 중심이, 10인치(25.4cm) 간격이 되도록 적용되었다. 야안을 상기 테이프의 상층부에 감았다. 모든 필라멘트가 제위치에 확실히 고정되도록 단일 스틱(코팅된) 마스킹 테이프가 상기 야안-커버된 더블 스틱 테이프상 적용되었다. 상기 야안-커버된 Halar

필름은 상기 드럼으로부터 절단되고 각 테이프의 중심선을 따라 절개되었다. 그 결과물은 Halar

필름으로 뒤를대고 있으며 한쪽 말단에 1인치(2.45cm) 폭 테이프로 고정된, 8인치(20.3cm) 길이의 평행한건조 야안 공급물이었다.The yarn was wound around the rotating drum of the filament winder. The drum had a diameter of 30 inches (76 cm) and a length of 48 inches (122 cm) before winding and Halar, a copolymer of chloro, trifluoro ethylene and ethylene before winding

It was wrapped in a film (AlliedSignal Specialty Flm, of Pottsville, Pennsylvania). A strip of 2-inch (5.08 cm) wide double stick tape was applied so that the center of the core was spaced 10 inches (25.4 cm) parallel to the axis of the drum. The yarn was wound around the upper layer of the tape. A single stick (coated) masking tape was applied on the yarn-covered double stick tape so that all the filaments were secured in place. The Ya'an-covered Halar

The film was cut from the drum and cut along the centerline of each tape. The result is Halar

It was an 8 inch (20.3 cm) parallel dry eye feed, backed with film and secured with 1 inch (2.45 cm) wide tape at one end.

B. Fabrication of Experimental Shield Panels

필름은 상기 섬유 방향에 대하여 90°회전되었다. 1/8인치(0.3175cm) 두께의 알루미늄 플레이트, 7.5인치×7.5인치(19cm×19cm)를 상기 야안상 중심에 놓고 그 어셈블리를 120℃, 3톤 수압 프레스에 10분간 방치하였다. 금속 플레이트는 상기 섬유망을 둘러싸는 테이프의 압반을 깨끗이하기위한 스페이서로서 작용하였다.An 8 inch (20.3 cm) long section of Step A was placed on top of the metal sheet and taped in place to properly secure the eye. A matrix resin is applied (see Examples for details) and a second 8 inch (20.3 cm) section is placed on the first 8 inch (20.3 cm) section, which is Halar at the top layer.

The film was rotated 90 ° with respect to the fiber direction. A 1/8 inch (0.3175 cm) thick aluminum plate, 7.5 inch by 7.5 inch (19 cm by 19 cm), was placed in the center of the eye field and the assembly was left to stand in a 120 ton, 3 ton hydraulic press for 10 minutes. The metal plate acted as a spacer to clean the platen of the tape surrounding the fiber network.

C. Measure the flexibility of the panel

As body armor, the panel of the present invention should have similar or greater flexibility than conventional ballistic resistant fabric structures. A simple test to measure flexibility is to place a square panel on a flat surface and have one side edged by a length (l) (panel side parallel to the edge). The vertical distance h with respect to the unsupported side of the panel on a flat surface is measured and the value of (h / l) is calculated. The panel is very flexible when h / l is 1 and the panel is very rigid when h / l is zero. To compare the flexibility of the control fabric with the flexibility of the panel, the percent flexibility is calculated as follows:

100% × (h / l) _panel / (h / l) _fabric =% flexibility

With body armor, it is desirable that the panel has a percent flexibility of about 50-150%, preferably about 70-150% and more preferably about 85-150% of the matrix-free control ballistic resistant fabric as described in Example 10.10 below. desirable. Preferably the h / l is about 0.7 or more, more preferably about 0.85 or more.

Hereinafter, the present invention will be described in detail through examples.

Example 1

Spectra®1000 (215 denier, 60 filaments per end) fiber (40 EPI (ends per inch) and nominal density (AD) are 0.00376 gm commercially available from AlliedSignal Inc. (Peterburg, Virginia) / Cm2) and granular, type G1650 Kraton® rubber matrix resins (particles passed through # 30, 600 micrometers or 0.0234 inch screens) manufactured by Shell Chemical Co. (Houston, Texas). Was used. The matrix resin was sprinkled at 7.5 wt% (total) on the lower net before cross-plying. After molding, the matrix resin spot connected the islands and fiber strands of the filament in the fiber strands. The panel was initially paper-like, but after crimping and flexing, it was fabric-like.

Example 2

Example 1 was repeated with 15 wt% of matrix resin. The results were the same as in Example 1, but the panel was more robust and the resilient to delamination was excellent.

Example 3

Example 1 was repeated with a matrix resin of 20 wt%, with an additional polyethylene film ply of 0.00035 inch (0.000889 cm) thickness manufactured by Raven Industries (Sioux City, South Dakota) located on both sides of the fiber mesh. (Halar® film was removed and placed on the PE film before the released paper was pressed). The panel is flexible and has a robust structure.

Example 4

Spectra® 1000/215/60 fiber (40 end per inch) and nominal surface density (AD) of 0.00376 gm / cm3 and Kraton® D1107 rubber manufactured by Pierce & Stevens (Buffalo, New York) Prinlin B7137X-1 matrix resin was used for the test procedure. Prinlin was sprayed into fine droplets on both sides of the web of the fibrous network so that the fibers were 85% by weight and dried before molding. The panel was initially paper-like, but with fabric-like flexibility after crimping and flexing.

Example 5

Spectra® 1000/215/60 fiber (40 EPI (ends per inch) and nominal surface density (AD) of 0.00376 gm / cm 3) and diluted matrix resin consisting of 3 parts of water and 1 part of Prinlin B7137X-1 were tested. Used in the procedure. Prinlin was sprayed onto the web's both sides of the fiber with fine droplets so that the fibers were 95% by weight and dried before molding. The panel was initially paper-like, but with fabric-like flexibility after crimping and flexing. The panel was not as robust as the panel of Example 4.

Example 6

120 micron / fines polyethylene manufactured from Spectra® 1000/215/60 fibers (40 end per inch) and nominal surface density (AD) of 0.00376 gm / cm3 and PFS Thermoplastic Powder Coatings Inc. (Big Spring, Texas) Roto-molding powder S3DSBK matrix resin was used for this test procedure. PE was sprayed onto the lower fibrous mesh before shaking and cross-flying so that the total PE measured after molding was 14 wt% of the total weight. The panels were initially paper-like, but were fabric-like by manipulation. Made of low friction surface.

Example 7

Spectra® 1000/215/60 fibers (40 ends per inch and nominal surface density (AD) of 0.00376 gm / cm3) and a single polyethylene film 0.00035 inch (0.000889 cm) thick, manufactured by Raven Industries, between the two fibres Used as the reference for Example 6. The panel was less flexible than the panel of Example 6, but useful.

Example 8

Spectra®1000 / 215/60 fibers (40 ends per inch (EPI) and nominal surface density (AD) of 0.00376 gm / cm 3) were used without matrix resin. After molding, the panels showed paper-like quality and were separated during operation.

Example 9

AlliedSignal Inc. Product Spectra®1000 / 1300, 240 filaments per end (9.25EPI (ends per inch) and nominal surface density (AD) of 0.005266 gm / cm3) were sprayed with Prinlin B7137X-1 matrix resin and dried prior to molding to allow fibers to It was processed according to the above test procedure to be in weight%. The panels were very flexible compared to similar continuous fiber matrix articles with equivalent fiber surface densities.

Example 10

Example 10.1-10.3: A thermoplastic elastomer monofilament was prepared by injection molding a 2: 1 weight ratio mixture of two thermoplastic elastomers (Kraton® G1652 and 1657). Elastomer fibers, 650 and 1300 deniers, were formed from uni-directional tapes as follows: Halar® film along the length of the drum on the drum, 19 inches (48.26 cm) from center to center. It was positioned using a double-sided adhesive tape having a width of 2 inches (5.08 cm) fixed to be. The thermoplastic elastomeric fibers were wound to a width of 4.6 ends / inch (1.81 ends / cm). One-sided adhesive tape was attached onto the two-sided tape so that the ends of the fibers were fixed in place. The middle of the fixing tape was cut down so that the webs were 17 inches (43.18 cm) in length in the available single direction fiber mats held together in separate rubber strips. The web was cut at intervals of 17 inches (43.18 cm) along the length direction to produce 17 square inches (43.18 cm 3) of single-directional fiber mat with significant spacing between single filaments. Spectra® fiber tape in a uniform orientation was made in the same manner except that a 1300 denier Spectra®1000 was wound on the drum at 2.6ends / inch (1.02ends / cm). Stabilized composite panels were prepared by cross-flying the rubber mats with Spectra® tape and molding them together at 100 ° C. for 5 minutes at a pressure of 10ton / ft ² (1.076 × 10 ⁵ kg / m 2). The stabilized panels are then cross-plyed, and the Halar® film is removed and then molded together with the resin-rich sides of the stabilized uniform-oriented tape facing the panels together (stable single orientation). Same conditions as in the tape production). The results are shown in Table 1 below.

TABLE 1

Comparison of Ballistic Performance of Flexible Body Armor at Surface Density of 1 kg / ㎡ for 38-caliber Lead Bullets-Rubber Grid Reinforcement

Specimen Matrix (kg / ㎡) Fiber wt% Panel No. V ₅₀ (ft / s) SEAT (J㎡ / kg) # 10.1 (4.6ends / in) 1.04 81 8 890 377 # 10.2 (2.3ends / in) 1.05 80 8 807 295 # 10.3 (4.6ens / in) 1.24 66 8 802 247

Comparing 10.1 to 10.2, equal weight percentages of elastomeric grids indicate that the fiber grids are more effective. The additional elastomer grid stiffens the panel and also reduces ballistic efficiency (10.3). The results indicate that grid weight percent and size need to be optimized for optimal protection against certain ballistic risks.

D1107용액으로 코팅되었다. 건조 챔버를 통과하며 용매가 제거되고 단일-방향 테이트 물질이 제조되는 섬유망은 균일하게 코팅된다. 이 물질은 교차-플라이되며 폴리에틸렌 필름을 상부와 하부바닥 표면에 라미네이트되어 패널이 서로 달라붙는 것을 방지한다. 패널, 섬유, 매트릭스 및 PE 필름의 면밀도는 각각 0.147, 0.105, 0.0262 및 0.0157kg/㎡이었다. PE필름의 융점은 114℃였다. 10.4: Comparative example: Parallel fibrous mesh (commercially available from AlliedSignal, trade name Spectra Shield® (single component, 1300 denier yarn of Spectra®1000 fiber, 240 filaments per yarn) Kraton dissolved in cyclohexane

Coated with D1107 solution. The fibrous network through which the solvent is removed and where the uni-directional tate material is produced is uniformly coated. The material is cross-ply laminated to a polyethylene film on the top and bottom surfaces to prevent the panels from sticking together. The surface densities of the panels, fibers, matrices and PE films were 0.147, 0.105, 0.0262 and 0.0157 kg / m 2, respectively. The melting point of the PE film was 114 ° C.

10.5. Halar® films made by AlliedSignal Specialty Films were wound around 4 ft. (121.92 cm) in length and 30 in. (76.2 cm) in diameter. The drum was rotated to wind the Spectra® 1000 fibers (1300 denia) to 9.26ends / in. (3.65ends / cm). The fiber network was sprayed with latex (Pierce and Stevens. Prinlin B7137X-1, Kraton® D1107: rosin 3: 1 weight ratio). This single-directional tape backed with Halar was cut to 15 square inches (38.1 cm 2) and 0/90 cross-ply with latex inside. The panels were then molded at 125 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 5 kg / m 2) so that the fibers were 81% by weight. All assemblies were molded as described above except the Halar® film was removed and the polyethylene film (same as used in Example 10.4) was placed on the outside of the 0/90 panel and the molding time was 2 minutes.

10.6: A polyethylene film (same as the film used for the panel of Example 10.5) was wound on a drum 4 ft. (121.92 cm) long and 30 in. (76.2 cm) in diameter, and the latex was 125-250 microns in band width on its surface. Specimens were prepared as in Example 10.5, except that the film was sprayed to cover about 25% of the film surface with the circular domain of the elastomer. The spraying process was performed with a Wagner Power Painter-Model 310 using a 0.8 mm nozzle. Spraying started at one end of the rotating drum and proceeded to the other end, forming a separate circular domain of Kraton D1107. Spectra 1000 fibers were wound in the same manner as in Example 10.5. A robust, uniform-direction tape was made. The 0/90 panel series was molded with polyethylene fibers on its surface. Molding was performed at 80 ° C., 95 ° C., 105 ° C. and 130 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 ⁵ kg / m 2). As the molding temperature increased, the panels became more paper-like and less fabric-like in flexibility. One 0/90 panel was molded (0.075 inches (0.191 cm) thick, 0.87 inches (2.21 cm) outside diameter and 0.37 inches (0.94 cm) inside diameter) to fit the washing machine array. Fully consolidated washer forms were imprinted on the panels. This demonstrates that the combined pattern can be produced from the panel of the present invention. Useful domain structures can be configured to provide a continuous line (such as an equilateral triangle array) that is easily folded. Eight panels molded at 95 ° C. were tested for .38 caliber lead bullets using Example 10.6. Furthermore, one panel was placed in a spot joining mold with a square grid with raised circular portions at the grid intersections. The circular portion had a diameter of 1.0 mm and a center-to-center distance of 7 mm. The panels were placed in a press of about 500 psi and molded at 115 ° C. for 150 seconds. The panel maintains flexibility. This molding method can produce various patterns.

10.7: 8.03ends / in (3.16ends / cm) on a drum rotating 1500 denier aramid fibers, Twaron fibers (Akzo products, 1450 denier yarns, 1.5 denier per filament, tensile strength 24.4 g / denier, modulus 805 g / denier) A specimen was prepared in the same manner as in Example 10.6, except that the specimen was wound. Circular domains were formed on the polyethylene film as in Example 10.6. The part was also formed by spraying on the twisted fiber network in the same manner as in Example 10.6. Scanning electron microscopy indicates that the coated portion is discontinuous. The part was 150-500 microns in size and very long in a direction parallel to the fiber length l. L / D ratios vary from 3: 1 to 25: 1 for these domains.

10.8: Thermoplastic elastomer fibers were prepared by injection molding a 2: 1 weight ratio mixture of Kraton® G1652 and 1657. Mono-directional tape was formed from elastomeric fibers (650 denier) as follows:

Thermoplastic elastomer monofilaments were prepared by injection molding a mixture of thermoplastic elastomers (Kraton® G1652 and 1657) in a 2: 1 weight ratio. Elastomeric fibers of 650 and 1300 denia were formed of a single-direction tape as follows: The Halar® film was fixed on the drum along a longitudinal direction with a center-to-center spacing of 19 inches (48.26 cm). It was positioned using a double sided adhesive tape having a width of 2 inches (5.08 cm). The thermoplastic elastomeric fibers were wound to a width of 4.6 ends / inch (1.81 ends / cm). The one-sided adhesive tape was attached in place of the two-sided tape such that the ends of the fibers were fixed in place. The middle of the fixing tape was cut down so that the filaments were webs of 17 inches (43.18 cm) in length in a single, available fiber mat held with each other in separate rubber sty. The web was cut at lengths of 17 inches (43.18 cm) in the longitudinal direction to produce 17 square inches (43.18 cm 3) of single-direction fiber mats with significant spacing between single filaments. A single-way Spectra® fiber tape was made in the same manner except that a 1300 denier Spectra®1000 was wound on the drum at 2.6ends / inch (1.02ends / cm). Stabilized composite panels were prepared by cross-flying the rubber mats with Spectra® tape and molding them together at 100 ° C. for 5 minutes at a pressure of 10ton / ft ² (1.076 × 10 ⁵ kg / m 2). The stabilized panels are then cross-plyed, the Halar® film is removed and then molded together with the resin-rich sides of the stabilized uniform-oriented tape facing the panels together (stabilized single-directional Same conditions as the tape production).

A single-way Spectra® fiber tape was prepared in the same manner except that the 1300 Denia Spectra®1000 was wound on a drum at 9.26ends / in. (3.65ends / cm).

Stabilized single-directional tape panels were prepared by cross-flying rubber and Spectra® panels and molding them together at 100 ° C. for 5 minutes at 10 ton / ft ² (1.076 × 105 kg / cm 2). These stabilized single-tapes are cross-plyed, and the Halar® film is removed and then stabilized single-directional with the resin-rich sides of the stabilized single-directional tape facing the panels. It was molded together under the same conditions used to make the tape.

10.9: Water vapor delivery

Compared to the Spectra Shield® material, the relative performance of water vapor transmission through the panel of the present invention (Example 10.3) is 2 oz. 15 g of water was placed in a container (42 mm inside diameter), and the loss weight was measured after 24 hours at 50% relative humidity at room temperature. The panel was secured around the container using double adhesive tape. Spectra®1000 ballistic fabric (Style 955-215 Denia, plain weave 55 x 55 ends / in. (21.7 x 21.7 ends / cm)) was also tested. Water vapor was permeated to the structure of the present invention to a degree similar to that of the fabric. The results are shown in Table 2 below.

[Table 2] Comparison of water loss

Specimen Loss Wt Wt. % Loss ^* Norm-top opening 8.05 g 100 Single filament (Example 10.4) 0.01 g 0.12 Grid coalesced (Example 10.3) 1.6 g 20 Spectra fabric 2.39 g 30

% Weight loss is 100 x Ws / Wc, which is the weight loss in the opened container and given conditions, respectively.

10.10: Flexibility

Flexibility of commercially available monocomponent, grid-reinforced panels (Example 10.3) and commercially available Spectra®1000 fabrics (Clark-Schwebel, 215 Denia, Spectra®1000 / 45x45 ends / inch (17.32 x 17.72 ends / cm) plain weave) Was compared. The specimens were placed on a flat surface and the edges were stretched to a length of 13 cm (l). The distance h below the flat surface of the free side was measured. The larger the distance h, the more flexible the structure. As can be seen in Table 3, nonwoven panels with grids were more flexible than woven Spectra®1000 ballistic fabrics. The specimens were bent to wear out before testing.

TABLE 3

Panel Flexibility Comparison

Specimen Length (l) (cm) Height (h) (cm) h / l Flexibility% Monocomponent 13 4 0.3077 36 Ballistic Fabric 13 11.0 0.8462 100 Grid Coated Panel 13 11.5 0.8846 104

Example 11

11.1: Halar® film made by AlliedSignal Specialty Films was wound around a drum 4 ft. (121.92 cm) in length and 30 in. (76.2 cm) in diameter. A double-sided adhesive tape strip having a width of 2 inches (5.08 cm) was applied along the drum length at intervals of 8 inches (20.32 cm). The drum was rotated to wind the Spectra® 1000 fibers (1300 denia) to 9.26ends / in. (3.65ends / cm). After winding the Spectra® 1000 eye, a 2 in (5.08ends / cm) masking tape strip was applied on the area covered with double-sided adhesive tape to ensure the fibers were securely in place. The adhesive tape along with the Halar® film and the Spectra® fiber was cut down into the fiber network along the centerline of the adhesive tape to produce a mat having a fiber length of 8 inches (20.32 cm) and a width of 48 inches (121.92 cm). Furthermore, the mat was cut into sizes convenient for use with elastomeric fibers. The polymer was injection molded through a 0.02 in. (0.051 cm) die at 260 ° C. using an Instron capillary rheometer to prepare Kraton® G1650 (2212) denier, a single filament elastomeric fiber. Eight square inches (20.32 cm 2) of parallel fiber nets were attached to the metal plate and the double-sided adhesive tape was placed on both sides of the web in the tape length direction parallel to the fiber length direction. Kraton® G1650 fibers were placed perpendicular to the fiber direction and taped on both sides of the web at 1 cm intervals.

A robust single-directional tape was molded between metal plates with Halar® film on one side and formed at 125 ° C. at low pressure in a hydraulic press and then the film was removed. The tape was cross-plyed and remolded to produce 0/90 panels with a total surface density of 0.154 kg / cm 2 and a matrix of 32 wt%. The width of the modified Kraton G1650 fiber was about 3 mm, corresponding to 49% surface coverage. After the first few bends, a flexible, low friction panel was produced. During the molding process, Spectra® fibers are warped, voids are removed and the initial stiffness is greater than with flexible materials.

11.2: The specimens of this example were the same as in Example 11.1, except that the Kraton® fibers were cut 3 cm in length and placed irregularly on the fibrous network. Thereafter, it was molded to produce a single-direction tape. The Kraton® G1650 flow exhibited an undesirable phenomenon in which the fiber network was significantly warped.

11.3: This example is identical to Example 11.1 except that the elastomeric fibers are extruded through a 0.007 inch die at 260 ° C. The mono-directional tape and the resulting 0/90 cross-plyed panel matrix were both 5.5 wt%. The surface density of the 0/90 panel was 0.1113 kg / m <2>. The elastomeric fibers widened to less than 1 mm, with the result that the coverage of the elastomer was 20% of the panel area.

11.4: Same as Example 11.1 except that the elastomeric fibers (Kraton® G1651, 811 denier) were oriented 45 degrees in the longitudinal direction of the Spectra® fibers. The elastomeric fibers were extruded through a 0.012 in. (0.0305 cm) die at 260 ° C. The mono-directional tape and the resulting 0/90 cross-plyed panel matrix were both 20 wt%. Two different structures are possible, forming the elastomeric fibers in a diamond form or a series of lines parallel to 45 degrees to the Spectra® fiber length. When a lot of resin is pressed against each other, the final molded panel is agglomerated and very low in friction.

Example 12

The tape was made by the following method: A PE film of 0.00035 in. (0.000889 cm) thickness made by Raven Industries, Sioux City, South Dakota, was placed in a drum: statically uniform by rotating the drum and spraying the latex onto the film surface. To form a dispersed dispersed dispersion: Spectra® fiber 1000/650 denia, 240 filaments per end, were then wound on a drum; Latex was sprayed onto the Spectra® fiber.

These tapes were robust enough to make and handle the final cross-fried panels suitable for bulletproof vest applications. Tape in a single direction was cross-ply (0/90) and molded under different conditions. Cross-plyed panels generally exhibit both good flexibility and good ballistic performance. The cross-plyed panels indicate that the amount, consolication and distribution of the matrix can be adjusted according to the properties required for the particular application.

12.1: Parallel fiber nets were uniformly coated with a kraton® D1107 solution dissolved in cyclohexane and then passed through a drying chamber to remove solvent to prepare a single-directional tape material. The material was cross-flyed and laminated with 0.00035 in. (0.000889 cm) of polyethylene film made by Raven Industries (Sioux City, South Dakota) to the top and bottom surfaces of the surface to prevent the panels from sticking together. Molding conditions were 10 minutes at 120 degreeC. The surface densities of the panels, fibers, matrices and PE films were 0.147, 0.105, 0.0262 and 0.0157 kg / m 2, respectively. The PE film had a melting point of 114 ° C. Polyethylene films have increased weight and strength compared to matrix Kraton® D1107 alone.

12.2: Matrix Existing as Discontinuous Thermoplastic Part

Halar® film (AlliedSignal Specialty Films, Pottsville, PA) was wound around a drum 4 ft. (121.92 cm) long and 30 in. (76.2 cm) in diameter. The drum was rotated to wind the Spectra® 1000 fibers (1300 denia) to 9.26ends / in. (3.65ends / cm). The fibrous mesh was sprayed with latex (Kraton® D1107 and Prinlin B7137X-1 from Pierce and Stevens at a 3: 1 weight ratio). This single-way tape was cut 15 square inches (38.1 cm 2) with Halar® backing and 0/90 cross-ply inside with tape. The cross-flyed material was then molded at 125 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 ⁵ kg / m 2). Same method as the first molding, except the Halar® film was removed and the polyethylene film (same as the film used in Example 12.1) was placed on the outer surface of the 0/90 panel and all assemblies were molded for 2 minutes. Molded into. Eight panels of 15 square inches (38.1 cm 2) were laminated to each other, clamped and tested for clay backing using 0.38 caliber lead bullets (158 grains). The V ₅₀ value was 824 ft / s (251.2 m / s).

12.3: Kraton® D1107 and Prinlin matrix domain 8 panel with PE film (the matrix part is sprayed), 81% fiber weight and ADT = 1.04 kg / m2

In this example, the specimen was wound with a polyethylene film (equivalent to the film on the panel surface of Example 12.2) on a metal drum (length 4 ft. And diameter 30 in.) And the latex was sprayed onto the surface (sprayed Kraton® sprayed on the surface). / Prinlin matrix was prepared in the same manner as in Example 12.2 except that the surface density of 0.0019kg / ㎡). The circular domain of the elastomer in the plane was 125-250 microns in size and the coverage of the film surface was about 25%. The spraying process was performed with a Wagner Power Painter-Model 310 using a 0.8 mm nozzle. Spraying was done starting at one end of the rotating drum and proceeding to the other end to provide a separate circular matrix domain. Spectra® 1000 fibers were wound in the same manner as described in Example 12.2, and the fiber mat was also sprayed in the same manner as in Example 12.2. This resulted in a robust, single-way tape with release backing removed. A polyethylene film was molded on the surface of the 0/90 panel series. Molding was performed at 80 ° C., 95 ° C., 105 ° C. and 130 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 ⁵ kg / m 2). As the molding temperature increased, the panels became more paper-like and less fabric-like in flexibility. The molded panels at 95 ° C. were bent for several hours and evaluated for flexibility by the method described in Example 10.10. The flexibility of the panel was 0.96 and the percent flexibility compared to ballistic fabrics was 114% (see Example 10.10).

One 0/90 panel was molded (0.075 inches thick, 0.87 inches outside diameter and 0.37 inches inside diameter) to fit the washing machine array. The fully integrated washing machine was stamped on the panel. This demonstrates that the combined pattern can be produced from the panel of the present invention. Useful domain structures that provide continuous lines that fold easily (such as an equilateral triangle array) can be easily constructed.

Eight panels molded at 95 ° C. were tested for 0.38 caliber lead bullets. Moreover, one panel was placed in a spot bonding mold with a square grid with raised domains at the grid intersections (the circle was 1.0 mm in diameter and the center-to-center distance was 7 mm). The panels were placed in a press of about 500 psi and molded at 115 ° C. for 150 seconds. The circular portion remained coalesced (about 1.6 area percent) and the remaining area remained un coalesced. The panel remained flexible.

12.4: This example was prepared by the method described in example 12.3.

TABLE 4

Ballistic Performance Comparison of Finite Body Armor for 0.38 Caliber Lead Ballistic

Specimen ADT (kg / ㎡) Fiber wt% V ₅₀ (ft / s) [m / s] SEAT (J㎡ / kg) Domain 12.1 1.05 72 720 [219.5] 234 None 12.2 1.04 81 824 [251.2] 310 U 12.3 1.24 81 789 [240.5] 296 U 12.4 1.04 78 858 [261.5] 327 U

Example 13

The following structure was investigated:

A. Single Ingredient Spectra Shield® Material

This structure, incorporating 0/90 prepregs, requires PE films on its top and bottom to prevent fusion of the panel due to the adhesion of the matrix (Kraton® D1107). The panels are agglomerated and relatively low in fiber wt% (72%). This sandwich structure impairs flexibility as shown in Table 5.

B. Minor Modification of a Single Component to Improve Performance

The basic idea is to substitute the matrix domain for continuous matrix alignment in the commercial product A to increase flexibility. Kraton® D1107 latex was sprayed through a paint sprayer onto a fibrous network in a rotating drum to effect a static uniform distribution. This process is very simple and forms domains on the surface of the fiber mat. Resin-rich surfaces were integrated and PE films were placed on top and bottom. This assembly was molded to produce a flexible panel and laminated to produce a ballistic target with 81% by weight of fibers. Referring to Table 5, it can be seen that the ballistic (SEAT) efficiency is about 1.3 times that of the commercially available standard (A) and the fiber weight% is significantly higher than that of the commercially available products.

C. Matrix-PE Powder Designed for Rotational Molding

The best ballistic results were obtained with this system. Linear low density polyethylene powder (Tm = 105 ° C.) was pumped into the slurry on a fiber mat in a rotating drum. The 0/90 panels thus produced are flexible and have low surface friction. The advantage of PE powder is that it is inexpensive and no solvent is used in the manufacturing process. Referring to Table 5, the ballistic performance (SEAT) was very good compared to the standard specimen A.

D (1) -D (2). Matrix EPDM / PE Powder with Weight Ratio 1: 4

Since the powder tends to fall off the drum without sticking to the fiber, some difficulties arise in producing parallel fiber networks with PE powder. The PE powder slurry mixed with the EPDM solution was found to adhere well to the fiber mat in the rotating drum. However, the ballistic performance is not so good as to be obtained when the PE powder is used alone.

Table 5 summarizes the ballistic efficiencies of these test materials based on their SEAT values.

TABLE 5

Comparison of Ballistic Performance of Flexible Body Armor to 0.38 Caliber Lead Ballistic

Specimen ADT Fiber wt% V ₅₀ (ft / s) [m / s] SEAT (J㎡ / kg) area   A (normative) 1.05 72 720 [219.5] 234 None B 1.04 81 824 [251.2] 310 Oil C 0.981 88 854 [260.3] 353 Oil D (1) 1.00 85 774 [235.0] 283 Oil D (2) 1.04 80 750 [ 228.6] 257 u

Example 14

Aramid fiber reinforced flexible targets were prepared as described in Example 12.3. Twaron fibers (Akzo, 1450 denia, 1.5 denier per filament, tensile strength 24.4 g / denier, modulus 805 g / denier) were used in place of the Spectra ® 1000 eyepiece and wound on the drum at 8.3 turns per inch. Ballistics were tested on .38 lead bullets of the target with seven 0/90 panels with ADT = 0.995kg / m 2. V ₅₀ was 924 ft / s (281.6 m / s) and SEAT was 408 J-Kg / m 2. The structure of this embodiment provides excellent ballistic protection.

Example 15

15.1: Halar® film (AlliedSignal Specialty Films, Pottsville, PA) was wound around a drum 4 ft. (121.92 cm) in length and 30 in. (76.2 cm) in diameter. The drum was rotated to wind the PBZO fibers (1300 denia) to 9.26ends / in. (3.65ends / cm). The fibrous mesh was sprayed with latex (Kraton® D1107 and Prinlin B7137X-1 from Pierce and Stevens at a weight ratio of 3: 1). This single-way tape was cut 15 square inches (38.1 cm 2) with Halar® backing and 0/90 cross-ply inside with tape. The cross-flyed material was then molded at 125 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 ⁵ kg / m 2). The Halar® film was removed and the polyethylene film was placed on the outer surface of the 0/90 panel and all assemblies were molded. Eight panels of 15 square inches (38.1 cm 2) were laminated to each other, clamped and tested for clay backing using .38 caliber lead bullets (158 grains). The V ₅₀ value is expected to be large compared to a significant amount of PBZO fibers in conventional shielded-style products.

Example 16

16.1: Halar® film (AlliedSignal Specialty Films, Pottsville, PA) was wound around a drum 4 ft. (121.92 cm) in length and 30 in. (76.2 cm) in diameter. The drum was rotated to wind the PBZT fibers (1300 denier) to 9.26ends / in. (3.65ends / cm). The fibrous mesh was sprayed with latex (Kraton® D1107 and Prinlin B7137X-1 from Pierce and Stevens at a 3: 1 weight ratio). This single-way tape was cut 15 square inches (38.1 cm 2) with Halar® backing and 0/90 cross-ply inside with tape. The cross-flyed material was then molded at 125 ° C. for 15 minutes at 10 tons / ft ² (1.076 × 10 ⁵ kg / m 2). The Halar® film was removed and the polyethylene film was placed on the outer surface of the 0/90 panel and all assemblies were molded. Eight panels of 15 square inches (38.1 cm 2) were laminated to each other, clamped and tested for clay backing using .38 caliber lead bullets (158 grains). The V ₅₀ value is expected to be large compared to a significant amount of PBZT fibers in conventional shielded-style products.

The detailed description, drawings, and examples of the invention illustrate the scope of the invention and thus do not limit the invention.

Claims (26)

A plurality of filaments and a plurality of matrix islands, each matrix island connecting at least two filaments, each matrix island having an average size of less than 5 mm, and a final volume ratio of the matrix islands to the plurality of filaments being 0.5 Or less than, wherein the matrix islands hold multiple filaments together in a single structure. The composite of claim 1, wherein the plurality of filaments are arranged planar, essentially parallel. The composite of claim 1, wherein the plurality of filaments comprise filaments having an average tensile modulus of 300 g / denier or greater and an average tenacity of 7 g / denier or greater. The composite of claim 1, wherein the final volume ratio of matrix islands to multiple filaments is 0.4 or less. 5. The composite of claim 4, wherein the final volume ratio of the matrix islands to the plurality of filaments is 0.25-0.02. 6. The composite of claim 5 wherein the final volume ratio of matrix islands to multiple filaments is 0.2-0.05. The method of claim 1, wherein the filament is an ultra high molecular weight polyethylene having a molecular weight of 500,000 or more, an ultra high molecular weight polypropylene having a molecular weight of 750,000 or more, aramid, polyvinyl alcohol, polyacrylonitrile, polybenzoxazole, polybenzothiazole And a filament selected from the group consisting of glass fibers, ceramics and mixtures thereof. 8. The composite of claim 7, wherein said plurality of filaments comprise ultra high molecular weight polyethylene having a molecular weight of 500,000 or more. 9. The composite of claim 8 wherein the ultra high molecular weight polyethylene filament has a stiffness of 30 g / denier or more and a tensile modulus of 1500 g / denier or more. 8. The composite of claim 7, wherein said plurality of filaments comprise aramid. The composite of claim 1, wherein the matrix island comprises a flexible composition selected from the group consisting of elastomers, thermoplastic elastomers, thermoplastic resins, thermosetting resins, and mixtures thereof. 12. The composite of claim 11 wherein said matrix island comprises an elastomer. 12. The composite of claim 11, wherein said matrix island comprises a mixture of two or more elastomers, thermoplastic elastomers and thermoplastic resins. The composite of claim 1 wherein said domain matrix provides a filament of robust structure. The composite of claim 1, wherein each filament in the composite is in contact with at least one matrix island. The composite of claim 15 comprising a plurality of matrix islands in a predetermined pattern. The composite according to claim 1, wherein the filaments are arranged in parallel in one direction. 2. The composite of claim 1 wherein the average size of the matrix islands is less than 3 mm in planar dimension. 2. The composite of claim 1 wherein the average size of the matrix islands is less than 1 mm in planar dimension. The composite of claim 1 wherein the composite has at least 70% flexibility of a plain weave with 45 x 45 ends per 2.54 cm (1 in.) Made of ultra high molecular weight polyethylene yarn having a Spectra®1000 molecular weight of 500,000 or greater. Complex made with. The composite of claim 1, wherein the composite has a flexibility of at least 0.7. The complex of claim 1, wherein the complex has a flexibility of at least 0.85. 23. The composite according to any one of claims 1 to 22, wherein the composite has a ballistic performance (SEAT) value for a lead bullet impact of 0.38 diameter 158 grains of 257 J-m 2 / kg or more. . A multilayer fibrous web comprising a plurality of filaments; And A plurality of matrix islands connecting the at least two filaments, the average size being less than 5 mm; A composite having a V ₅₀ value greater than a composite of the same area having a continuous polymer matrix for 0.38 diameter 158 grain lead bullets; delete delete

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